Methods for producing bioderived propylene glycol

ABSTRACT

In the process of distilling a polyol product mixture including one or both of a biobased propylene glycol and a biobased ethylene glycol from the reaction of hydrogen with a biobased feed, it has been discovered that undesirable epoxides can form, and the present invention provides means for guarding against their formation, for removing epoxides which do form by particular methods of distilling, and for removing the epoxides from a finished, otherwise commercially acceptable biobased glycol product.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No.14/002,160, filed Oct. 10, 2013.

TECHNICAL FIELD

This invention relates generally to processes for making a bioderivedpropylene glycol. More particularly, the present invention relates tomethods for making a bioderived propylene glycol through the reaction ofa biobased feedstock—conventionally, glycerol or five and six carbonsugars and/or sugar alcohols—with hydrogen to provide a polyol productmixture including propylene glycol, wherein the polyol product mixtureis further processed to yield a commercially acceptable biobasedequivalent to the petroleum-based or -derived commodity propylene glycolproduct used today in so many different applications.

BACKGROUND

The present invention is concerned with the development of renewablysourced products which are able to serve as commercially acceptable,drop in replacements for materials, and especially commodities such aspropylene glycol and ethylene glycol, which are presently madedownstream of conventional fossil fuel operations. Such biobased,renewably sourced materials can be differentiated from theirpetroleum-derived counterparts, for example, by their carbon isotoperatios using ASTM International Radioisotope Standard Method D 6866, thedisclosure of which is incorporated by reference in its entirety. MethodD 6866 is based upon the fact that isotopic ratios of the isotopes ofcarbon within any given material, such as the 13 C/12 C carbon isotopicratio or the 14 C/12 C carbon isotopic ratio, can be determined usingcertain established analytical methods, such as isotope ratio massspectrometry, with a high degree of precision.

ASTM Method D6866, similar to radiocarbon dating, compares how much of adecaying carbon isotope remains in a sample to how much would be in thesame sample if it were made of entirely recently grown materials. Thepercentage is called the biobased content of the product. Samples arecombusted in a quartz sample tube and the gaseous combustion productsare transferred to a borosilicate break seal tube. In one method, liquidscintillation is used to count the relative amounts of carbon isotopesin the carbon dioxide in the gaseous combustion products. In a secondmethod, 13 C/12 C and 14 C/12 C isotope ratios are counted (14 C) andmeasured (13 C/12 C) using accelerator mass spectrometry. Zero percent14 C indicates the entire lack of 14 C atoms in a material, thusindicating a fossil (for example, petroleum based) carbon source. Onehundred percent 14 C, after correction for the post-1950 bomb injectionof 14 C into the atmosphere, indicates a modern carbon source. ASTM D6866 effectively distinguishes between biobased materials and petroleumderived materials in part because isotopic fractionation due tophysiological processes, such as, for example, carbon dioxide transportwithin plants during photosynthesis, leads to specific isotopic ratiosin natural or biobased compounds. By contrast, the 13 C/12 C carbonisotopic ratio of petroleum and petroleum derived products is differentfrom the isotopic ratios in natural or bioderived compounds due todifferent chemical processes and isotopic fractionation during thegeneration of petroleum. In addition, radioactive decay of the unstable14 C carbon radioisotope leads to different isotope ratios in biobasedproducts compared to petroleum products. As used herein, “biologicallyderived”, “bioderived”, and “biobased” may be used interchangeably torefer to materials whose carbon content is shown by ASTM D 6866, inwhole or in significant part (for example, at least about 20 percent ormore), to be derived from or based upon biological products or renewableagricultural materials (including but not limited to plant, animal andmarine materials) or forestry materials.

Propylene glycol and ethylene glycol have conventionally been producedfrom petrochemical sources. Commercial production of petroleum-based or-derived propylene glycol involves the hydration of propylene oxide,made predominantly by the oxidation of propylene. The commercialproduction of ethylene glycol similarly involves the hydration ofethylene oxide, made by the oxidation of ethylene. Propylene andethylene in turn are industrial by-products of gasoline manufacture, forexample, as by-products of fluid cracking of gas oils or steam crackingof hydrocarbons.

The world's supply of petroleum is, however, being depleted at anincreasing rate. As the available supply of petroleum decreases or asthe costs of acquiring and processing the petroleum increase, themanufacture of various chemical products derived therefrom (such aspropylene glycol and ethylene glycol) will be made more difficult.Accordingly, in recent years much research has taken place to developsuitable biobased propylene glycol and ethylene glycol products, whichcan be interchangeable with propylene glycol and ethylene glycolproducts deriving from petroleum refining and processing methods butwhich are made from renewable versus nonrenewable materials.

As a result of these efforts, processes have been developed by severalparties involving the hydrogenolysis of especially five and six carbonsugars and/or sugar alcohols, whereby the higher carbohydrates arebroken into fragments of lower molecular weight to form compounds whichbelong to the glycol or polyol family. Sugars containing five carbonchains, such as ribose, arabinose, xylose and lyxose, and correspondingfive carbon chain sugar alcohols such as xylitol and arabinitol, areamong the materials contemplated in U.S. Pat. No. 7,038,094 to Werpy etal., for example, as are six carbon sugars such as glucose, galactose,maltose, lactose, sucrose, allose, altrose, mannose, gulose, idose andtalose and six carbon chain sugar alcohols such as sorbitol. Some ofthese carbohydrate-based feedstocks are commercially available as pureor purified materials. These materials may also be obtained asside-products or even waste products from other processes, such as cornprocessing. The sugar alcohols may also be intermediate productsproduced in the initial stage of hydrogenating a sugar.

For other known examples of such processes, U.S. Pat. No. 5,206,927describes a homogeneous process for hydrocracking carbohydrates in thepresence of a soluble transition metal catalyst to produce lowerpolyhydric alcohols. A carbohydrate is contacted with hydrogen in thepresence of a soluble transition metal catalyst and a strong base at atemperature of from about 25° C. to about 200° C. and a pressure of fromabout 15 to about 3000 psi. However, as is evident from Tables II andIII in the disclosure of U.S. Pat. No. 5,206,927, about 2-7% of otherpolyol compounds are produced in the hydrocracking process. U.S. Pat.No. 4,476,331 describes a two stage method of hydrocrackingcarbohydrates using a modified ruthenium catalyst. European PatentApplications EP-A-0523 014 and EP-A-0 415 202 describe a process forpreparing lower polyhydric alcohols by catalytic hydrocracking ofaqueous sucrose solutions at elevated temperature and pressure using acatalyst whose active material comprises the metals cobalt, copper andmanganese. Still other examples of such carbohydrate-based processes maybe found without difficulty by those skilled in the art.

Other efforts have been based on the use of another readily accessiblebiobased feedstock, namely, glycerol. Glycerol is currently produced asa byproduct in making biodiesel from vegetable and plant oils, throughthe transesterification reaction of lower alkanols with higher fattyacid triglycerides to yield lower alkyl esters of higher fatty acids anda substantial glycerol byproduct. Glycerol is also available as aby-product of the hydrolysis reaction of water with higher fatty acidtriglycerides to yield soap and glycerol. The higher fatty acidtriglycerides may derive from animal or vegetable (plant) sources, orfrom a combination of animal and vegetable sources as well known, and avariety of processes have been described or are known.

In the context of vegetable oil-based biodiesel production and soapmaking, all sorts of vegetable oils have been combined with the loweraliphatic alcohols or water. Preferred vegetable oils include, but arenot limited to, soybean oil, linseed oil, sunflower oil, castor oil,corn oil, canola oil, rapeseed oil, palm kernel oil, cottonseed oil,peanut oil, coconut oil, palm oil, tung oil, safflower oil andderivatives, conjugated derivatives, genetically-modified derivativesand mixtures thereof. As used herein, a reference to a vegetable oilincludes all its derivatives as outlined above. For instance, the use ofthe term “linseed oil” includes all derivatives including conjugatedlinseed oil.

A biobased glycerol is also available as a product of the hydrogenolysisof sorbitol, as described in an exemplary process in U.S. Pat. No.4,366,332, issued Dec. 28, 1982.

U.S. Pat. Nos. 5,276,181 and 5,214,219 thus describe a process ofhydrogenolysis of glycerol using copper and zinc catalyst in addition tosulfided ruthenium catalyst at a pressure over 2100 psi and temperaturebetween 240-270° C. U.S. Pat. No. 5,616,817 describes a process ofpreparing 1,2-propanediol (more commonly, propylene glycol) by catalytichydrogenolysis of glycerol at elevated temperature and pressure using acatalyst comprising the metals cobalt, copper, manganese and molybdenum.German Patent DE 541362 describes the hydrogenolysis of glycerol with anickel catalyst. Persoa & Tundo (Ind. Eng. Chem. Res. 2005, 8535-8537)describe a process for converting glycerol to 1,2-propanediol by heatingunder low hydrogen pressure in presence of Raney nickel and a liquidphosphonium salt. Selectivities toward 1,2-propanediol as high as 93%were reported, but required using a pure glycerol and long reactiontimes (20 hrs). Crabtree et al. (Hydrocarbon processing February 2006 pp87-92) describe a phosphine/precious metal salt catalyst that permit ahomogenous catalyst system for converting glycerol into 1,2-propanediol.However, low selectivity (20-30%) was reported. Other reports indicateuse of Raney copper (Montassier et al. Bull. Soc. Chim. Fr. 2 1989 148;Stud. Surf. Sci. Catal. 41 1988 165), copper on carbon (Montassier etal. J. Appl. Catal. A 121 1995 231)), copper-platinum and copperruthenium (Montassier et al. J. Mol. Catal. 70 1991 65). Still otherhomogenous catalyst systems such as tungsten and Group VIIImetal-containing catalyst compositions have been also tried (U.S. Pat.No. 4,642,394). Miyazawa et al. (J. Catal. 240 2006 213-221) & Kusunokiet al (Catal. Comm. 6 2005 645-649) describe a Ru/C and ion exchangeresin for conversion of glycerol in aqueous solution. Again theirprocess however, results in low conversions of glycerol (0.9-12.9%).Again, still other examples of like processes may be found withoutdifficulty by those skilled in the art.

One of the recognized problems in producing a biobased propylene glycolor ethylene glycol by such methods, is that other diol compounds areformed which reduce the purity of the desired component. The boilingpoints of many of these components as shown in Table A are very close toone another, however, so that the separation of substantially purepropylene glycol from these other polyhydric alcohols is difficult.

TABLE A Polyols produced by Hydrocracking of Sorbitol Polyol WeightPercent Boiling Point, ° C. 2,3-Butanediol 3.5 182 Propylene glycol 16.5187 1,2-Butanediol 2.0 192 Ethylene glycol 25.2 198 1,3-Butanediol 2.7206 2,3-Hexanediol — 206 1,2-Pentanediol — 210 1,4-Pentanediol — 2201,4-Butanediol 2.1 230 1,5-Pentanediol 0.1 242 Diethylene glycol 2.2 2451,6-Hexanediol — 250 Triethylene glycol 2.1 285 Glycerin 38.8 2901,2,4-Butanetriol 4.8 190/18 mm

Several reports in the literature describe efforts for azeotropicallyseparating the other polyhydric alcohols from propylene glycol. Forinstance, U.S. Pat. No. 4,935,102 describes a method for using anazeotrope forming agent such as propylene glycol isobutyl ether,tetrahydrofurfuryl alcohol, N,N-dimethylacetamide, ethylene glycoldiethyl ether, diethylene glycol diethyl ether, 2-methoxyethyl ether,ethylene glycol n-butyl ether, diacetone alcohol and ethyl n-butylketone. In U.S. Pat. No. 5,423,955, the azeotrope forming agent consistsof a material selected from the group consisting of toluene, ethylbenzene, o-xylene, p-xylene, cumene, m-diisopropyl benzene, m-diethylbenzene, mesitylene, p-cymene, hexane, cyclohexane, methyl cyclohexane,heptane, 3-methyl pentane, octane, decane, 2,3,4-trimethyl pentane,dipentene, decalin, dicyclopentadiene, alpha-phellandrene, limonene,hemimellitene, myrcene, terpinolene, p-mentha-1,5-diene, beta-pinene,3-carene, 1-heptene, cyclopentane, pentane, o-diethyl benzene,2,2-dimethyl butane and 2-methyl butane. The azeotrope forming agentsdescribed in these two references may be characterized by their Hansensolubility parameters (Tables B and C), as these can be determined usingthe program “Molecular Modeling Pro Plus (version 6.0.6, NorgwynMontgomery Software Inc, available from ChemSW, Inc) based on valuespublished in the “Handbook of Solubility Parameters and OtherParameters” by Allen F. M. Barton (CRC Press, 1983) for solventsobtained experimentally by Hansen. The Hansen “h” (hydrogen bonding)values at 25° C. and Hansen “p” (polarity) values ° C. listed below werecalculated in this manner.

TABLE B Azeotropic agents used for separation of 2,3-Butanediol frompropylene glycol (U.S. Pat. No. 4,935,102). Azeotropic agent Hansen pHansen h Propylene glycol isobutyl ether 5.42 12.52 Tetrahydrofurfurylalcohol 10.46 10.96 N,N-dimethylacetamide 11.47 10.23 Toluene 0.75 1.98Ethyl benzene 0.65 1.85 p-Xylene 0.91 1.84 m-Xylene 0.91 1.84 o-Xylene0.91 1.84 Cumene 0.58 1.74 Mesitylene 0.98 1.7 Ethylene glycol diethylether 9.19 14.3 Diethylene glycol diethyl ether 9.22 12.332-Methoxyethyl ether 1.81 7.41 Ethylene glycol-n-butyl ether 5.13 12.27Diacetone alcohol 8.17 10.76 3-heptanone 5.28 3.93

TABLE C Azeotropic agents used for separation of 1,2-Butanediol fromethylene glycol (U.S. Pat. No. 5,423,955). Azeotropic agent Hansen pHansen h 3-Heptanone 5.28 3.93 Cyclohexanone 3.13 5.08 Diisobutyl ketone4.9 3.79 Methyl isoamyl ketone 6.03 4.2 Isobutyl heptyl ketone 3.76 3.312-Methoxyethyl ether 1.81 7.41 2,6-Dimethyl-4-heptanone 4.90 3.79p-Xylene 0.91 1.84 m-Xylene 0.91 1.84 o-Xylene 0.91 1.84 Ethyl benzene0.65 1.85 Cumene 0.58 1.74 Mesitylene 0.98 1.7

Alternative approaches to purifying the product mixture have beenproposed in commonly-assigned United States Patent ApplicationPublication US 2008/0275277A1 to Kalagias, published Nov. 6, 2008,wherein the addition of a polar solvent and extractive distillation arepresented as an alternative to the use of an azeotropic agent, and incommonly-assigned United States Patent Application PublicationUS2009/0120878A1 to Hilaly et al., published May, 14, 2009, whereinsimulated moving bed chromatography is offered as a means to achieve apurified, commercial grade biobased propylene glycol.

A difficulty that has not been appreciated before, though, is that indistilling out these other, undesired polyhydric alcohols, conditionscan be such that epoxides such as propylene oxide and glycidol can beformed. These two epoxides in particular are of concern for certainestablished uses and commercially important applications of propyleneglycol, at least for the reason that these substances are listed underthe State of California's “The Safe Drinking Water and Toxic EnforcementAct of 1986”—more commonly known as Proposition 65—as being known toCalifornia to cause cancer. Consequently, having a biobased, drop-inreplacement propylene glycol for a petroleum-based or -derived propyleneglycol will depend, for certain markets and end uses at least, ondeveloping a solution or solutions to this heretofore unrecognizedproblem.

SUMMARY OF THE INVENTION

The present invention addresses this difficulty by providing, accordingto a first aspect, a process for distilling a product mixture comprisedof biobased propylene glycol, biobased ethylene glycol or a combinationthereof and which further includes one or both of propylene oxide andglycidol, so that a distilled biobased glycol product stream is producedwhich is substantially free of both propylene oxide and glycidol.Epoxide removal is thus integrated into the refining process for a crudereaction product, to produce the desired biobased, commerciallyacceptable glycol product.

In other aspects, the present invention concerns other solutions thatcan be implemented independently of one another or especially given apreexistent refining process (that may or may not be feasibly adapted ormodified to carry out a distillation process according to the firstaspect), for example, a process for removing substantially all of thepropylene oxide and glycidol present in an otherwise finished, biobasedglycol product, as well as a process for guarding against and preferablysubstantially preventing the formation of propylene oxide and glycidolin a biobased glycol product from the distillation of the aforementionedproduct mixture. The present invention in this regard also contemplatesmeasures for both guarding against the formation of propylene oxide andglycidol in the biobased glycol product, as well as for treating thebiobased glycol product to ensure a biobased glycol product that issubstantially free of propylene oxide and glycidol.

DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts one embodiment of a distillation process that might beused according to the present invention.

FIG. 2 depicts an alternate embodiment of a distillation processaccording to the present invention.

FIG. 3 depicts a second alternate embodiment of a distillation processaccording to the present invention.

DETAILED DESCRIPTION

In its various embodiments, the present invention addresses the need fora biobased glycol product that is compliant with the requirements ofProposition 65 and preferably substantially free of propylene oxide andglycidol.

In one approach, the present invention addresses this difficulty byproviding, according to a first aspect, a process for distilling amixture containing propylene glycol, ethylene glycol, propylene oxide,glycidol and other monools and diols, such as a mixture obtained fromthe reaction of hydrogen with a sugar or sugar alcohol or with glycerolaccording to a method of the type described above.

In one embodiment 10 which is schematically depicted in FIG. 1, anaqueous reaction product 12 from the reaction of hydrogen 14 with anaqueous solution of biobased glycerol 16 according to a process of thetype described in United States Patent Application PublicationUS2008/0274019A1 to Beggin et al., published Nov. 6, 2008 and nowincorporated herein by reference—and of the same general character asprocessed in the commonly-assigned Kalagias and Hilaly et al.applications—is first distilled in columns 18 and 20 to remove lowmolecular weight alcohols (methanol, ethanol, propanols for example) andwater overhead in streams 22 and 24, respectively. The remainder 26 ispH modified with an acid 28 as described in the Beggin et al. reference,and then supplied as stream 30 to column 32, wherein components withboiling points higher than that of propylene glycol (unconvertedglycerol, mixed diols inclusive of the ethylene glycol formed in theprocess) are removed in stream 34. The distillate 36 is refined bydistillation in column 38 to produce a high purity propylene glycol as asubstantially water-free, bottoms product 40, with the glycidol andpropylene oxide being removed overhead in stream 42 with any residualwater and mixed diols. Stream 34 is preferably further processed bydistillation in column 44 to enable recovery of an ethylene glycol-richdiols mix overhead in stream 46 and unreacted glycerol for recycle asdesired in stream 48.

In another embodiment 70 of a distillation process, shown schematicallyin FIG. 2, an aqueous reaction product 72 from the reaction of hydrogen74 with an aqueous solution of biobased glycerol 76 is first pH modifiedby the addition at 78 of acid, preferably sulfuric acid, before beingsupplied as stream 80 to a first column 82. Lower molecular weightalcohols are distilled off in stream 84, then the remainder 86 proceedsto a second column 88 which operates to remove all but a small amount ofwater as stream 90. Column 92 separates out unreacted glycerol in abottoms stream 94, and the distillate 96 containing ethylene glycol,propylene glycol, higher diols (e.g., butanediols, pentanediols),propylene oxide, glycidol and less than one percent of water is furtherrefined by distillation in column 98, where ethylene glycol is firstseparated as a bottoms product 100. From the distillate 102, high puritypropylene glycol is separated out as a substantially propylene oxide-and glycidol-free, substantially water-free bottoms product 104, withthe propylene oxide, glycidol, 2,3-butanediol and any residual waterbeing removed overhead in stream 106.

Referring now to FIG. 3, in yet another embodiment 120 of a distillationprocess of the present invention according to a first aspect, an aqueousreaction product 122 from the reaction of hydrogen 124 with an aqueoussolution of biobased glycerol 126 is first pH modified by the additionat 128 of acid, preferably sulfuric acid, before being supplied asstream 130 to a first column 132. Lower molecular weight alcohols aredistilled off in stream 134, then the remainder 136 proceeds to a secondcolumn 138 which operates to remove all but a small amount of water asstream 140. Column 142 separates out unreacted glycerol in a bottomsstream 144, and the distillate 146 containing ethylene glycol, propyleneglycol, higher diols (e.g., butanediols, pentanediols), propylene oxide,glycidol and less than one percent of water is further refined bydistillation in column 148. Propylene oxide, glycidol, 2,3-butanedioland any residual water are distilled overhead from the column 148 instream 150, and the bottoms stream 152 containing ethylene and propyleneglycols is further distilled in column 154. A predominantly ethyleneglycol bottoms product 156 (with some residual propylene glycol) isrecovered from the column 154, while a high purity propylene glycolproduct 158 is recovered as a substantially glycidol- and propyleneoxide-free sidestream from the distillation. Some propylene glycol andresidual propylene oxide are carried overhead in 160 for being recycledback to column 142.

In each of these distillation embodiments, propylene oxide and glycidolare thus easily removed from the product mix resulting from thehydrogenolysis of a carbohydrate or polyol, according to any of thevarious references summarized above. In these distillations, thepropylene oxide and glycidol are removed in the distillates. Most of thepropylene oxide is removed with the lower molecular weight alcohols,whereas most of the glycidol is removed with the butanediols.

The present invention also provides a solution for removingsubstantially all of the propylene oxide and glycidol otherwise presentin a biobased glycol product, for example, after water, lower molecularweight alcohols, higher diols and unconverted glycerol have all beenremoved from an otherwise finished, purified and commercially suitablepropylene glycol product, by treating the otherwise finished biobasedglycol product with strong acid ion exchange resins. Resins suitable forthis application include any gel or macroporous (macroreticular) polymersuch as polystyrene or polystyrene/divinylbenzene that has beenfunctionalized with sulfonic acid. Examples of suitable commerciallyavailable resins presently meeting this description are AMBERLYST 15,AMBERLYST 35, AMBERLITE 200 H, DIAION UBK555 (H+ form), DOWEX 50W, DOWEX88(H+ form), and PUROLITE PD206. Typical conditions for the treatment ofepoxide-containing glycol product streams are flow rates of 1-5 bedvolumes/hr and temperatures of 50-120° C., preferably 60-100° C., andmost preferably 60-80° C.

A process for guarding against and preferably substantially preventingthe formation of propylene oxide and glycidol in a biobased glycolproduct from the distillation of the aforementioned product mixture,involves simply removing organic acid salts contained in the aqueousreaction product from the hydrogenolysis of a carbohydrate or of apolyol such as glycerol. Preferably all or substantially all of thesalts are so removed, for example, at least about 85 percent, morepreferably at least about 90 percent and most preferably more than about96 percent of the salts being removed. Surprisingly, these salts havebeen found to contribute to the production of epoxides such as propyleneoxide and glycidol in the distillation and refining of the aqueousreaction product. Separation and removal of these organic acid salts maybe accomplished by ion exclusion chromatography, using resins known tothose skilled in the art as suited for this purpose, for example, any ofthe various sodium or calcium form, strong cation exchangestyrene/polystyrene-divinylbenzene copolymer resins such as thoseavailable from The Dow Chemical Company under the trade designationsDOWEX 99/320, DOWEX 99/290, DOWEX N406, N306 AND N606, AMBERLITE CR1310,CR1320, C20N and IR 120, and AMBERJET 1000Na, 1300Na and 1500 Na, fromMitsubishi Chemical Company under the trade designations UBK550, UBK510Land UBK530, from The Purolite Company under the trade designations C100,PCR145, PCR450, PCR642, PCR732 and PCR833 or from a number of othermanufacturers. Simulated moving bed chromatography methods have beenfound useful for essentially continuously removing the salts, asexemplified below.

The bio-based propylene glycol, the bio-based ethylene glycol or thecombination thereof obtained by the processes of the present inventionmay be subjected to further purification or isolation techniques inorder to get a purity of at least 95%. In a further embodiment, thepurity may be obtained to at least 99.5% or even 99.7% depending on thedesired use of the bio-based propylene glycol, the bio-based ethyleneglycol or the combination thereof.

Further, those skilled in the art will appreciate that combinations ofthe measures offered above may be contemplated, for example, ionexclusion chromatography may be employed to remove organic acid saltsfrom the aqueous reaction product while one of the distillationsolutions or treatment with strong acid ion exchange resins may beadditionally undertaken to ensure a biobased glycol product that issubstantially free of the epoxides that would be present were suchmeasures not taken.

Still other refinements and modifications will be apparent to thoseskilled in the art given the embodiments that have been described aboveand in view of the examples that follow, and it is consequentlyunderstood that the present invention should not be taken as limited tothe particular embodiments or features of embodiments, or to anyparticular combination of features or details, except as expresslyrequired by the claims which follow.

With this caveat, the present invention is more particularly illustratedand understood by reference to the following examples:

Example 1

In this example, the removal of propylene oxide and glycidol aredemonstrated from two distillate streams containing propylene glycol(one actually obtained, and one synthesized/simulated to approximate adistillate stream obtainable from the aqueous reaction products from thehydrogenolysis of glycerol, as represented by aqueous reaction productsstream 12 in the description above) and from a lower alcohol/waterstream comprised of methanol and water.

Distillate stream A was thus comprised of a nonbiobased, commercialpropylene glycol doped with 100 parts per million by weight each ofpropylene oxide and glycidol, while distillate stream B was made up bydoping not more than about 10 ppm of propylene oxide and 250 ppm ofglycidol into a 2,3-butanediol cut from a distillation according toUnited States Patent Application Publication US 2008/0275277A1 toKalagias. Distillate stream C was made by doping 125 ppm of propyleneoxide and not more than about 10 ppm of glycidol into a methanol/waterstream.

An ion exchange column was assembled by loading 100 mL of DIAION® UBK555strongly acidic, food grade ion exchange resin from Mitsubishi ChemicalCompany or of AMBERLITE® 200H strongly acidic, food grade ion exchangeresin from The Dow Chemical Company into an Ace Glass #15 600 mmjacketed column. The column was connected to a MasterFlex 100RPM pumpand to reservoirs of Distillates A-C, the column jacket was thenconnected to a water bath. The resin column was washed in each iterationwith 10 bed volumes of deionized water at 5 bed volumes per hour (8.3mL/min), then 10 bed volumes of 5% hydrochloric acid solution werepassed through the column, and finally an additional 10 bed volumes ofdeionized water were pumped through the column to rinse residual acidfrom the resin in question.

Feeds of Distillates A-C were then pumped through the column at the same5 bed volumes per hour (corresponding to a column residence time of 12minutes) rate, and the treated distillates A-C were sampled at variousintervals, derivatized with diethyldithiocarbamate and analyzed fortheir epoxide content post-treatment, using the procedure described inVan Damme et al., “Determination of Residual Free Epoxide in PolyetherPolyols by Derivatization With DiethylammoniumN,N-diethyldithiocarbamate and Liquid Chromatography”, Journal ofChromatography A, col. 696, no. 1, pp 41-47 (1995). The initial samplingand analysis took place after the distillates in question had passedthrough a single bed volume of each resin, and then typically afterevery 5 to 80 bed volumes (or equivalently, after intervals of from 1 to16 hours on-stream).

It was determined by the initial sampling and analysis that there werein fact no detectable epoxides left in any of the treated DistillatesA-C after only a single pass, with the limits of detection being 100parts per billion for both epoxides in the PG product (Distillate A) bygas chromatography/mass spectroscopy, and 200-300 ppb for glycidol and100 ppb for propylene oxide in Distillates B and C by high performanceliquid chromatography (GC/MS not being well-suited for Distillates B andC because of confounding co-eluting peaks). This result demonstratesthat strong acid ion exchange resins are consequently very effective inremoving residual epoxides in the form of propylene oxide and glycidolfrom a bioderived propylene glycol.

Further sampling and analysis demonstrated that at 5 bed volumes/hr andunder the other stated conditions, the DIAION® UBK555 resin was mosteffective for Distillate A at a temperature of 80 degrees Celsius, forDistillate B at 60 degrees Celsius and for C at from 50 to 60 degreesCelsius. No breakthrough was seen in this regard for Distillates B and Cafter 500 bed volumes, while Distillate A showed no breakthrough after1600 bed volumes at 80 degrees Celsius. For the AMBERLITE® 200H resin,the preferred operating temperature was established at from 60 to 70degrees Celsius, and no breakthrough was observed after over 2000 bedvolumes had been processed of Distillate A, at 5 bed volumes per hourand at 60 to 70 degrees Celsius.

Example 2

A simulated moving bed apparatus was configured in a 1-1-5-5 sequence toremove organic salts from an unrefined/yet-to-be-distilled PG productstream from the hydrogenolysis of glycerol over a NiRe catalyst. Theapparatus employed 250 mL of DIAION® UBK550 sodium form, food grade ionexchange resin from Mitsubishi Chemical Company (the UBK550 gradecorresponding to the UBK555 resin in its sodium form) in each of thetwelve columns, on a carousel conventionally rotating opposite the flowof fluid through the apparatus. Five columns were used between the feedinlet to the carousel and the raffinate outlet, as an adsorption zonewherein the nonionic species (ethylene glycol, propylene glycol andglycerol) were more strongly retained and the organic salts enriched anddesorbed for being continuously removed in the raffinate stream. Fivecolumns were used between the purified, desalted product outlet and theunrefined PG feed inlet, in an enrichment zone wherein the organic saltswere desorbed and the more strongly retained glycol and glycerolcomponents enriched. One column was used between the inlet of the eluentdeionized water and the purified, desalted product outlet as adesorption zone, and finally, one column was interposed as a reload zonebetween the adsorption zone and the desorption zone, with just enoughflow through the column to displace the void fraction deionized waterfrom the column.

The step or switch time was set at 12 minutes, with unrefined PG productcontaining about 25 percent of PG entering the apparatus continuously inthe adsorption zone at 5.1 mL/minute. In a first run, deionized waterwas supplied as the eluent at 15.8 mL/minute, and the flow from thedesorption zone to the enrichment zone was set at 9.7 mL/minute whilethe flow from the adsorption zone to the reload zone was set at 4.4mL/minute. The raffinate and a desalted PG product flow rates from theapparatus were 10.4 and 10.5 mL/minute, respectively.

In this first run, 93.2 percent of the sodium salts were removed fromthe unrefined PG product into the raffinate, with an overall propyleneglycol yield of 99.2 percent in the desalted PG product compared to thePG fed into the apparatus. In a second run conducted after adjusting theeluent to 15.7 mL/minute and the flow rate from the desorption zone tothe enrichment section from 9.7 to 9.8 mL/minute, 96.2 percent of thesodium salts were removed into the raffinate, and 97.6 percent of the PGwas retained in the desalted PG product stream.

Example 3

An unrefined propylene glycol product was made by the hydrogenolysis ofa biobased glycerol over a Ni/Re catalyst. Approximately 5200 kg ofreactor product were neutralized over 19 batches. The average sulfuricacid dosage was 0.33 g/100 g of feed. There were two batches where thesulfuric acid loading was significantly less (0.03 g/100 g). The causewas undetermined, but may have been due to low concentration ofpropylene glycol due to start-up or shut down of the reactor. Theaverage pH of the reactor product was 12.1 and the average neutralizedpH was 6.9.

The thus-neutralized product was then distilled according to theembodiment shown in FIG. 2, beginning with an alcohol removal step. Thiscolumn was run under atmospheric pressure. Due to equipment constraintsa high reflux ratio was used. This resulted in less water overhead (4-12wt %) than indicated by process modeling (27 wt %). The propylene glycolyield was >99%. The other parameters are given in the table below.

TABLE 1 Alcohol Removal summary Alcohol Pilot ASPEN Rebolier temp 215218 F. Overhead temp 155-160 180 F. Overhead pressure atmosphericatmospheric Reboiler pressure atmospheric atmospheric PG yield >99% 100%Reflux ratio  70-400 10 Overhead H2O 4-12%   27% Bottoms Alcohol 100-200* 1000 ppm *as low as 10, one excursion as high as 800

The next step was a primary water removal step, designed to removesubstantially all of the water so that the bottoms to a subsequentglycerol removal step would contain less than 1 wt % of water. This stepwas completed successfully. The water concentration was brought down to0.6%. The propylene glycol yield was >99%. There were severaloperational problems due to salts in the reboiler and feed lines, butthese were mainly believed to be due to not having the correct steamflow or other operational issues. There was no evidence of solidsformation in the packing, which had been a concern with the low levelsof water targeted. The salts would wash out easily with water, and thecolumn was continuously run for approximately 5 days without havingproblems with the solids. The results are given in the table below.

TABLE 2 Water Removal Column (WRC) Performance WRC Pilot ASPEN Reboilertemp 340-355 342 F. Overhead temp 196-200 193 F. Overhead 20.4 20.4 Inof Hg pressure Reboiler 20.5-23   22.8 In of Hg pressure PG yield >99%100% Reflux ratio NA 0.4 reflux too low for pilot meter Bottoms H2O0.6-1.1  1%

The next separation was to remove the residual unreacted glycerol in aglycerol removal step. This step went very smoothly with no significantproblems. The yield was >99% with 0.5% glycerol in the distillate. Otherconditions and results were as reported in Table 3:

TABLE 3 Glycerol Removal Column (GRC) Performance GRC Pilot ASPENReboiler temp 322-338 323 F. Overhead temp 204-210 208 F. Overhead~1-2   0.8 In of Hg pressure Reboiler NA 1 In of Hg pressure PG yield >99% 100% Reflux ratio 1-4 0.4 Dist. Glycerol <0.5%  2%

Ethylene glycol was next to be separated out as a principal component ofthe PG product mixture. The results were not as good as hoped,unfortunately, primarily due to operational error. The goal was tomaximize yield and the distillate that went forward was not withinspecification (600 ppm on a propylene glycol basis). There was also oneupset that caused ethylene glycol at 1.2% to go forward. Propyleneglycol yield was between 95 and 98%, and the bulk product forward forthe subsequent butanediol removal step had 5700 ppm ethylene glycol and200 ppm 1,2-butanediol, as compared to the 500 ppm ethylene glycol and50 ppm 1,2-butanediol expected from modeling. During the run, theethylene glycol concentration was brought to approximately 45%,indicating that the amount of ethylene glycol in the feed has an effecton the propylene glycol yield. This column was run at 15.6 in Hgabsolute pressure. The results are given in the table below.

TABLE 4 Ethylene Glycol Removal Column (EGRC) Performance EGRC PilotASPEN Reboiler temp 341-346 326 F. Overhead temp 324-326 311 F. Overhead15.3 10.2 In of Hg pressure Reboiler pressure 16.6 11.2 In of Hg PGyield 95-98 90% Reflux ratio 3-8 8.5 Dist EG  1200-1700* 156 Bottoms EG  40-46% 22% *One run was as low as 540 ppm

The final distillation step undertaken was for the removal of2,3-butanediol (and 2,3-pentanediol and other lighter impurities). Thegoal of this step was to take USP grade propylene glycol as a bottomsproduct with less than 1000 ppm total butanediols and pentanediols. Thisspecification was met, even with the additional 1,2-butanediol fromerrors in the previous step. The yield was 95-97%. The column was run at10.7 in Hg absolute pressure. The final product had no detectableepoxides (0.2 ppm LOD). The results are summarized in the table below.The APHA color of the samples of the bottoms product was 3 and thespecification was 10. A sample of the final propylene glycol product wasgiven to a sensory group and found to be satisfactory.

TABLE 5 Butanediol Removal Column (BRC) Performance BRC Pilot ASPENReboiler temp 325 299 F. Overhead temp 197-218 264 F. Overhead pressure10.7 6.1 In of Hg Reboiler pressure 13.7-14   7.7 In of Hg PG yield  95-97% 97% Reflux ratio  80-90* 35 Bott total diols   950-1000** <1ppm *Reflux ratio will vary greatly due to the relatively low distillaterate **200 ppm was 1,2-BDO which is normally removed with EG, however anupset sent some forward.

What is claimed is:
 1. A process for distilling a product mixturecomprised of biobased propylene glycol, biobased ethylene glycol orcomprising both of these, and which further comprises one or both ofpropylene oxide and glycidol, including separating out the propyleneglycol and glycidol so that a distilled biobased glycol product isproduced which is substantially free of both propylene oxide andglycidol.
 2. A process according to claim 1, wherein the product mixtureis an aqueous reaction product from the reaction of hydrogen with anaqueous solution of biobased glycerol, and wherein the distillation ofthe product mixture includes: distilling low molecular weight alcoholsinclusive of methanol, ethanol and any propanols overhead in a firstcolumn; distilling substantially all of the water from the first columnbottoms overhead in a second column; modifying the pH of the secondcolumn bottoms with acid, and then removing substantially all of thecomponents therein with higher boiling points than that of propyleneglycol in the bottoms from a third column; and distilling the overheadsfrom the third column in a fourth column to produce the distilledbiobased propylene glycol product as the bottoms, with removing anyglycidol and propylene oxide contained in the third column overheads asthe overheads from the fourth column.
 3. A process according to claim 2,further comprising distilling the third column bottoms to produce anethylene glycol-rich diols mix overhead and a bottoms containingunreacted glycerol for recycle and reuse.
 4. A process according toclaim 1, wherein the product mixture is an aqueous reaction product fromthe reaction of hydrogen with an aqueous solution of biobased glycerol,and wherein the distillation of the product mixture includes: modifyingthe pH of the product mixture by addition of an acid before distillingthe product mixture in a first column to produce an overheads with lowermolecular weight alcohols inclusive of methanol, ethanol and anypropanols; distilling overhead all but a small amount of the water inthe first column bottoms, in a second column; distilling the secondcolumn bottoms in a third column, to separate out unreacted glycerol forrecycle in the third column bottoms and provide a distillate overheadcomprised of ethylene glycol, propylene glycol, C₄ and higher diols,propylene oxide, glycidol and less than one percent of water; distillingthe third column overheads in a fourth column, to produce an ethyleneglycol-rich bottoms and fourth column overheads; and distilling thefourth column overheads to produce a distilled biobased propylene glycolproduct which is substantially free of both propylene oxide and glycidolas well as being substantially water-free, and an overheads comprised ofpropylene oxide, glycidol, residual water and C₄ and higher diols.
 5. Aprocess according to claim 1, wherein the product mixture is an aqueousreaction product from the reaction of hydrogen with an aqueous solutionof biobased glycerol, and wherein the distillation of the productmixture includes: modifying the pH of the product mixture by addition ofan acid before distilling the product mixture in a first column toproduce an overheads with lower molecular weight alcohols inclusive ofmethanol, ethanol and any propanols; distilling overhead all but a smallamount of the water in the first column bottoms, in a second column;distilling the second column bottoms in a third column, to separate outunreacted glycerol for recycle in the third column bottoms and provide adistillate overhead comprised of ethylene glycol, propylene glycol, C₄and higher diols, propylene oxide, glycidol and less than one percent ofwater; distilling the distillate overhead from the third column toproduce a fourth column overheads comprising propylene oxide, glycidol,C₄ and higher diols and residual water, and bottoms comprised ofethylene and propylene glycols; distilling the fourth column bottoms ina fifth column, wherein a predominantly ethylene glycol bottoms isproduced, a substantially propylene oxide-, glycidol- and water-freedistilled propylene glycol product is recovered as a sidestream, andpropylene glycol and residual propylene oxide are recovered overhead forbeing recycled back in a recycle loop to the feed for the thirddistillation column.
 6. A process for removing substantially all of thepropylene oxide and glycidol from a finished, industrial orpharmaceutical grade biobased propylene glycol product, comprising thesteps of determining the content of propylene oxide and glycidolimpurities in the propylene glycol product and contacting the propyleneglycol product with a strong acid ion exchange resin for a time andunder conditions sufficient to reduce the levels of propylene oxide andglycidol present to below detection limits.
 7. A process according toclaim 6, wherein the strong acid ion exchange resin is a food graderesin.
 8. A process according to claim 6, wherein one or both ofpropylene oxide and glycidol are present in the untreated biobasedpropylene glycol product at more than 100 parts per million, and aftertreatment have a corresponding concentration or concentrations of lessthan 100 parts per billion.
 9. A process according to claim 6, whereinthe untreated biobased propylene glycol product is both substantiallycolorless and substantially odorless.
 10. A process for guarding againstthe formation of propylene oxide and glycidol in a biobased glycolproduct from the distillation of an aqueous product mixture comprised ofbiobased propylene glycol, biobased ethylene glycol or comprising bothof these, comprising removing organic acid salts contained in theaqueous product mixture through ion exclusion chromatography.
 11. Aprocess according to claim 10, wherein the aqueous product mixture isthe result of the hydrogenolysis of a carbohydrate or a polyol.
 12. Aprocess according to claim 10, wherein at about 85 percent of the saltsare removed before the product mixture is distilled.
 13. A processaccording to claim 12, wherein at least about 90 percent of the saltsare removed.
 14. A process according to claim 13, wherein at least about96 percent of the salts are removed.
 15. A process according to claim10, wherein the ion exclusion chromatography is accomplished in asimulated moving bed system.
 16. A biobased propylene glycol or ethyleneglycol with no detectable amounts of oxiranes contained therein.